JP7151856B2 - glass article - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for manufacturing a glass article having an organic film, and a glass article having an organic film.

In the process of manufacturing various glass articles, it is often necessary to separate and collect one or more glass articles from a large glass plate, a so-called separation step.

In such a separation process, a scribe line is formed at a predetermined position on the main surface of the glass sheet by mechanical processing, and then a bending moment is applied to the glass sheet along the scribe line to divide the glass sheet. operations are often performed.

Also, recently, a method has been proposed in which a glass plate is irradiated with a _CO2 laser, which is a gas laser, and the incident heat from the _CO2 laser cuts the glass plate to a predetermined size to separate and collect glass articles. (for example, Patent Document 1). As another method for separating and collecting such glass articles, a gas laser such as an excimer laser, an Ar laser, or a He—Ne laser, a solid laser such as a YAG laser, a semiconductor laser, or a free electron laser can be used. There is a way to use

JP 2012-526721 A

As described above, there is known a method of separating a glass article from a glass plate by irradiating the glass plate with a laser and fusing the glass plate at a predetermined position.

However, many glass articles have various organic films on their main surfaces. For example, when manufacturing a cover glass for a portable electronic device, an organic film such as an anti-fingerprint film (AFP) may be placed on the glass plate. If a separation process as in Patent Document 1 is performed on a glass plate having such an organic film, there may arise a problem that the organic film may be damaged by incident heat from the laser, particularly at the end face.

In order to deal with this problem, it is conceivable to separate the glass substrate from the glass plate and then form an organic film on each separated glass substrate.

However, in such a method, it is necessary to handle a large number of glass substrates in the film forming process, which complicates the process and reduces the efficiency of manufacturing glass articles. Therefore, this method does not provide a fundamental solution to the aforementioned problems.

The present invention has been made in view of such a background. It aims at providing the manufacturing method of a glass article. Another object of the present invention is to provide a glass article in which damage to the organic film is significantly suppressed.

In the present invention, there is provided a method for manufacturing a glass article having an organic film, comprising:
(1) In a glass plate having a first main surface and a second main surface facing each other, by irradiating a laser from the first main surface side of the glass plate, the first main surface , an in-plane void region in which a plurality of voids are arranged is formed, and a plurality of internal voids in which one or more voids are arranged from the in-plane void region toward the second main surface a step in which columns are formed;
(2) forming an organic film on the first main surface or the second main surface of the glass plate;
(3) irradiating and scanning the main surface side of the glass plate on which the organic film is formed with a laser different from the laser along the in-plane void region or its vicinity, separating one or more glass articles along the in-plane void regions;
has
In the step (3), a manufacturing method is provided in which the another laser is irradiated so as to satisfy the following conditions:
In the separated organic film of the glass article, when the central portion on the first main surface side is MC and one point on the end surface of the glass article is MP when viewed from above (however, the glass article is a polygon, MP is selected from points excluding the intersection of two sides),
In the MP, the count number of fluorine obtained by the X-ray photoelectric spectroscopy (XPS) method is I _MP (F), the count number of silicon is I _MP (Si), and I _MP (F)/I _MP (Si) is _RMP , and
At the point MC, the count number of fluorine obtained by the X-ray photoelectric spectroscopy (XPS) method is I _MC (F), the count number of silicon is I _MC (Si), and I _MC (F)/I _MC ( When Si) is _RMC ,

Ratio R _MP /R _MC ≧0.3

meet.

Moreover, in the present invention,
A method for producing a glass article having an organic film, comprising:
(1) forming an organic film on the first main surface of a glass plate having a first main surface and a second main surface facing each other;
(2) By irradiating a laser from the first main surface side of the glass plate, an in-plane void region in which a plurality of voids are arranged is formed on the first main surface, and the surface forming a plurality of rows of internal voids in which one or more voids are arranged from the internal void region toward the second main surface;
(3) irradiating and scanning the first main surface side of the glass plate with a laser different from the laser along the in-plane void region or its vicinity, thereby removing the in-plane void region from the glass plate; separating one or more glass articles along
has
In the step (3), a manufacturing method is provided in which the another laser is irradiated so as to satisfy the following conditions:
In the separated organic film of the glass article, when the central portion on the first main surface side is MC and one point on the end surface of the glass article is MP when viewed from above (however, the glass article is a polygon, MP is selected from points excluding the intersection of two sides),
In the MP, the count number of fluorine obtained by the X-ray photoelectric spectroscopy (XPS) method is I _MP (F), the count number of silicon is I _MP (Si), and I _MP (F)/I _MP (Si) is _RMP , and
At the point MC, the count number of fluorine obtained by the X-ray photoelectric spectroscopy (XPS) method is I _MC (F), the count number of silicon is I _MC (Si), and I _MC (F)/I _MC ( When Si) is _RMC ,

Ratio R _MP /R _MC ≧0.3

meet.

Furthermore, in the present invention, a glass article having an organic film,
The glass article is
a glass substrate having first and second major surfaces facing each other and an end surface;
an organic film disposed on the first main surface of the glass substrate;
has
In the organic film, when the central portion on the side of the first main surface is MC, and one point on the end face in top view is MP (however, when the first main surface is substantially polygonal, MP is selected from points excluding the intersection of two sides),
In the MP, the count number of fluorine obtained by the X-ray photoelectric spectroscopy (XPS) method is I _MP (F), the count number of silicon is I _MP (Si), and I _MP (F)/I _MP (Si) is _RMP , and
At the point MC, the count number of fluorine obtained by the X-ray photoelectric spectroscopy (XPS) method is I _MC (F), the count number of silicon is I _MC (Si), and I _MC (F)/I _MC ( When Si) is _RMC ,

Ratio R _MP /R _MC ≧0.3

A glass article is provided that satisfies:

INDUSTRIAL APPLICABILITY The present invention can provide a method for manufacturing a glass article that can significantly suppress damage to the organic film present on the main surface when the glass article is separated from the glass plate. Moreover, the present invention can provide a glass article in which damage to the organic film is significantly suppressed.

BRIEF DESCRIPTION OF THE DRAWINGS It is the figure which showed typically the flow of the manufacturing method of the glass article by one Embodiment of this invention. It is a figure showing typically the form of the glass plate which can be used in the manufacturing method of the glass article by one embodiment of the present invention. FIG. 3 is a schematic diagram for explaining the forms of an in-plane void region and an internal void array; FIG. 4 is a diagram schematically showing one form of an in-plane void region; FIG. 2 is a diagram schematically showing a state in which a plurality of in-plane void regions are formed on the first main surface of the glass plate; FIG. 4 is a diagram schematically showing an example of an in-plane void region; FIG. 4 is a diagram schematically showing another example of an in-plane void region; FIG. 4 is a diagram schematically showing the concentration profile of introduced ions in the in-plane direction (corresponding to the thickness direction of the glass plate) of the imaginary end surface according to one embodiment of the present invention. FIG. 4 is a diagram schematically showing a state in which an organic film is formed on the first main surface of the glass plate; FIG. 4 is a diagram schematically showing a state in which an organic film is formed on the first main surface of the glass plate; FIG. 4 is a diagram schematically showing a state in which an organic film is formed on the first main surface of the glass plate; FIG. 4 is a diagram schematically showing the flow of another method for manufacturing a glass article according to one embodiment of the present invention; 1 is a schematic perspective view of a glass article according to one embodiment of the invention; FIG. FIG. 14 is a schematic cross-sectional view of the glass article along line AA of FIG. 13; FIG. 4 is a diagram showing an example of XPS analysis results of an organic film of a sample according to Example 1;

An embodiment of the present invention will be described below with reference to the drawings.

(Method for producing a glass article according to one embodiment of the present invention)
A method for manufacturing a glass article according to an embodiment of the present invention will be described with reference to FIGS. 1 to 11. FIG.

FIG. 1 schematically shows a flow of a method for manufacturing a glass article according to one embodiment of the present invention (hereinafter referred to as "first manufacturing method").

As shown in FIG. 1, the first manufacturing method includes:
(1) a laser irradiation step (step S110) of irradiating a glass plate having a first main surface and a second main surface facing each other with a laser from the first main surface side of the glass plate; ,
(2) a film forming step (step S120) of forming an organic film on the first main surface or the second main surface of the glass plate;
(3) A separation step of irradiating the main surface side of the glass plate on which the organic film is formed with a laser different from the laser to separate one or more glass articles from the glass plate (step S130 )When,
have

Each step will be described below with reference to FIGS. 2 to 11 are diagrams schematically showing one step of the first manufacturing method.

(Step S110)
First, a glass plate having first and second major surfaces facing each other is prepared.

The glass composition of the glass plate is not particularly limited. The glass plate may be, for example, soda lime glass, alkali aluminosilicate glass, or the like.

The thickness of the glass plate is not particularly limited, but may be in the range of 0.03 mm to 6 mm, for example.

FIG. 2 schematically shows an example of the form of the glass plate 110. As shown in FIG. The glass plate 110 has a first major surface 112 and a second major surface 114 facing each other, and an end surface 116 .

Note that the form of the glass plate 110 is not particularly limited. For example, the glass plate 110 may have various shapes such as a substantially rectangular shape as shown in FIG. 2, a polygonal shape, an elliptical shape (including a circular shape), and the like.

Next, the glass plate 110 is irradiated with a laser. One main surface (here, as an example, the first main surface 112) of the glass plate 110 is irradiated with the laser. It should be noted that the laser used here is different from the _CO2 laser used in the subsequent separation step (step S130).

In-plane void regions are formed in first main surface 112 of glass plate 110 by laser irradiation. Also, a plurality of internal void rows are formed downward from this in-plane void region, that is, toward the second main surface 114 side.

Here, the “in-plane void region” means a linear region formed by arranging a plurality of surface voids in a predetermined arrangement. In addition, the “internal void row” is a linear region formed by arranging one or more voids from the first main surface 112 toward the second main surface 114 inside the glass plate. means.

The forms of the "in-plane void region" and the "internal void array" will be described in more detail below with reference to FIG. FIG. 3 schematically shows in-plane void regions and internal void arrays formed in the glass plate.

As shown in FIG. 3 , the glass plate 110 has one in-plane void region 130 and a plurality of internal void rows 150 corresponding to the in-plane void region 130 .

As described above, the in-plane void region 130 means a linear region in which a plurality of surface voids 138 are arranged in a predetermined arrangement. For example, in the example of FIG. 3, a plurality of surface voids 138 are arranged in a certain direction (X direction) on the first main surface 112 of the glass plate 110, thereby forming the in-plane void regions 130. .

Each surface void 138 corresponds to a laser irradiation location on the first major surface 112 and has a diameter of, for example, between 1 μm and 5 μm. However, the diameter of the surface void 138 varies depending on the laser irradiation conditions, the type of the glass plate 110, and the like.

A center-to-center distance P between adjacent surface voids 138 is arbitrarily determined based on the composition and thickness of the glass plate 110, laser processing conditions, and the like. For example, the center-to-center distance P may range from 2 μm to 10 μm. Note that the center-to-center distance P between the surface voids 138 does not need to be equal at all positions, and may differ from place to place. That is, surface voids 138 may be arranged at irregular intervals.

On the other hand, the internal void array 150 is formed by arranging one or more voids 158 from the first main surface 112 toward the second main surface 114 inside the glass plate 110 as described above. linear region.

The shape, size and pitch of voids 158 are not particularly limited. Voids 158 may be circular, oval, rectangular, or triangular in shape, for example, when viewed in the Y direction. In addition, the maximum dimension of the voids 158 when viewed in the Y direction (usually corresponding to the length of the voids 158 along the extending direction of the internal void row 150) is, for example, in the range of 0.1 μm to 1000 μm. There may be.

Each surface void 138 forming the in-plane void region 130 has a corresponding internal void row 150 . For example, in the example shown in FIG. 3, a total of 18 internal void rows 150 corresponding to 18 surface voids 138 are formed.

Note that in the example of FIG. 3 , the voids 158 forming one internal void row 150 are arranged along the thickness direction (Z direction) of the glass plate 110 . That is, each internal void row 150 extends in the Z direction. However, this is merely an example, and the voids that make up the internal void array 150 may be arranged from the first major surface 112 to the second major surface 114 in a state that is inclined with respect to the Z direction.

Also, in the example of FIG. 3, each internal void row 150 is composed of an arrangement of a total of three voids 158 excluding surface voids 138 . However, this is merely an example, and each internal void row 150 may consist of one or two voids 158, or four or more voids 158. FIG. Also, the number of voids 158 included in each internal void row 150 may be different. Additionally, some voids 158 may be connected with surface voids 138 to form “long” surface voids 138 .

Furthermore, each internal void row 150 may or may not have voids (second surface voids) opened at the second major surface 114 .

As is clear from the above description, the in-plane void region 130 is not a region actually formed as a continuous “line”, but a virtual void formed when the surface voids 138 are connected. Note that it represents a linear region.

Similarly, it should be noted that the internal void array 150 does not represent an area actually formed as a continuous "line", but an imaginary linear area formed by connecting the voids 158. There is

Furthermore, a single in-plane void region 130 need not necessarily be identified as a "line" (row of surface voids 138), but rather a single in-plane void region 130 located in close proximity to each other. may be formed as a collection of parallel "lines" arranged side by side.

FIG. 4 shows an example of an in-plane void region 130 recognized as an aggregate of such multiple “lines”. In this example, two parallel surface void rows 138A and 138B are formed on the first main surface 112 of the glass plate 110, and these form one in-plane void region 130. . The distance between the rows of voids 138A and 138B on both surfaces is, for example, 5 μm or less, preferably 3 μm or less.

In the example of FIG. 4, the in-plane void region 130 is composed of two rows of surface voids 138A and 138B, but the in-plane void region 130 may be composed of more rows of surface voids. .

Hereinafter, such an in-plane void region composed of a plurality of rows of surface voids is particularly referred to as a "multi-line in-plane void region". In addition, the in-plane void region 130 composed of one row of surface voids as shown in FIG. 3 is particularly referred to as a "single-line in-plane void region" to be distinguished from a "multi-line in-plane void region".

In-plane void region 130 and internal void array 150 as described above can be formed by irradiating first main surface 112 of glass plate 110 with a laser under predetermined conditions.

More specifically, first, a first position on the first main surface 112 of the glass plate 110 is irradiated with a laser, thereby extending from the first main surface 112 to the second main surface 114 to the first main surface 112 . A first row of internal voids is formed that includes surface voids. Next, by changing the irradiation position of the laser on the glass plate 110 and irradiating the second position of the first main surface 112 of the glass plate 110 with the laser, the second main surface 112 is irradiated with the laser. A second row of internal voids is formed across the surface 114 including a second surface void. By repeating this operation, an in-plane void region 130 and a corresponding internal void array 150 can be formed.

Note that if a single laser irradiation does not form an internal void row having voids 158 sufficiently close to the second main surface 114 , that is, if the voids 158 that are closest to the second main surface 114 are not formed. , if still sufficiently far from the second major surface 114 (e.g., in the void closest to the second major surface 114, the distance from the first major surface 112 is one thickness of the glass sheet 110). /2 or less), laser irradiation may be performed two or more times at substantially the same irradiation position. Here, "substantially the same (irradiation) position" means that the two positions are not only perfectly matched, but also that they are slightly deviated (for example, a maximum deviation of 3 μm).

For example, laser irradiation was performed multiple times along a first direction parallel to the first main surface 112 of the glass plate 110 to form a first in-plane void region 130 and an internal void row 150 corresponding thereto. After (first pass), laser irradiation (second pass) is performed in substantially the same direction and at substantially the same irradiation position as in the first pass, thereby making the first in-plane void region 130 corresponding to the first in-plane void region 130 deeper. , an internal void array 150 may be formed.

Although it depends on the thickness of the glass plate 110, the distance from the center of the void 158 that constitutes the inner void row 150 that is closest to the second main surface 114 to the second main surface 114 is , 0 μm to 10 μm.

Lasers that can be used for such processing include, for example, short-pulse lasers with pulse widths on the order of femtoseconds to nanoseconds, ie, 1.0×10 ⁻¹⁵ to 9.9×10 ⁻⁹ seconds. Such short-pulse laser light is preferably a burst pulse in that internal voids are efficiently formed. In addition, the average output during the irradiation time of such a short pulse laser is, for example, 30 W or more. If the average output of the short-pulse laser is less than 10 W, sufficient voids may not be formed. As an example of burst pulse laser light, a burst laser with 3 to 10 pulses forms one internal void train, the laser output is about 90% of the rated (50 W), the burst frequency is about 60 kHz, and the burst time. Widths may range from 20 picoseconds to 165 nanoseconds. A preferred range for the duration of the burst is 10 nanoseconds to 100 nanoseconds.

In addition, as a laser irradiation method, there are a method of using self-convergence of a beam based on the Kerr-Effect, a method of using a Gaussian-Bessel beam with an axicon lens, and a line-focusing beam formed by an aberration lens. There are methods. In any case, any method may be used as long as an in-plane void region and an internal void array can be formed.

For example, when a burst laser device is used, the dimensions of the voids forming the internal void array 150, the number of voids 158 included in the internal void array 150, and the like can be changed to some extent by appropriately changing the laser irradiation conditions. be able to.

In the following description, a plane including the in-plane void region 130 and the internal void row 150 corresponding to the in-plane void region 130 (a hatched plane 165 in FIG. 3) is referred to as a “virtual end face. ”. This imaginary end face 165 substantially corresponds to the end face of the glass article manufactured by the first manufacturing method.

As an example, FIG. 5 schematically shows a state in which a plurality of in-plane void regions 130 are formed on the first main surface 112 of the glass plate 110 .

In the example of FIG. 5, five in-plane void regions 130 are formed in the first main surface 112 of the glass plate 110 in the horizontal direction (X direction) and five in the vertical direction (Y direction). Although not visible from FIG. 5 , one or more voids intermittently extend toward the second main surface 114 below each in-plane void region 130 , that is, on the side of the second main surface 114 . A plurality of rows of internal voids are formed.

In FIG. 5, three-dimensional portions partitioned by two longitudinally adjacent in-plane void regions 130 and laterally adjacent two in-plane void regions 130 of the glass sheet 110 and internal void rows corresponding to these, that is, 4 A virtual minimum unit surrounded by two virtual end faces is called a glass piece.

The shape of the in-plane void region 130 and thus the shape of the glass piece 160a substantially correspond to the shape of the glass article obtained after step S130. For example, in the example of FIG. 5, 16 rectangular glass articles are finally manufactured from the glass material 110 . Also, as described above, the imaginary end face 165 including each in-plane void region 130 and the corresponding internal void row 150 corresponds to one end face of the glass article manufactured after step S130.

It should be noted that the shape and arrangement of the glass pieces 160a shown in FIG. 5 are merely examples, and they may be formed in a predetermined shape and arrangement according to the shape of the final glass article.

6 and 7 schematically show an example of an assumed in-plane void region and another form of the glass piece.

In the example of FIG. 6, each in-plane void region 131 is arranged as a single substantially rectangular closed line (loop) and has curved portions at the corners. Therefore, the glass piece 160b surrounded by the in-plane void regions 131 and the internal void rows (not visible) has a substantially rectangular plate shape with curved corners.

In addition, in the example of FIG. 7, each in-plane void region 132 is arranged as one substantially elliptical closed line (loop). Accordingly, the glass piece 160c has a substantially disk-like shape.

Also, in these examples, one imaginary end face forms a continuous end face of the glass article, so that the resulting glass article has only one end face.

As such, the in-plane void regions 130, 131, 132 may be formed in a straight line, a curved line, or a combination of both. Also, the glass pieces 160a, 160b, and 160c may be surrounded by a single virtual end face or by a plurality of virtual end faces.

(Chemical strengthening treatment)
When glass plate 110 contains an alkali metal, chemical strengthening treatment may be performed on glass plate 110 after step S110 and before step S120.

In the chemical strengthening treatment, the glass plate is immersed in a molten salt containing an alkali metal, and alkali metal ions with a smaller atomic diameter existing on the surface of the glass plate 110 are converted into alkali metal ions with a larger atomic diameter existing in the molten salt. It is the process of replacing metal ions.

Conditions for the chemical strengthening treatment are not particularly limited. The chemical strengthening treatment may be performed, for example, by immersing the glass plate 110 in molten salt at 430° C. to 500° C. for 1 minute to 2 hours.

Nitrate may be used as the molten salt. For example, when replacing the lithium ions contained in the glass plate 110 with larger alkali metal ions, a molten salt containing at least one of sodium nitrate, potassium nitrate, rubidium nitrate, and cesium nitrate may be used. Further, when replacing the sodium ions contained in the glass plate 110 with larger alkali metal ions, a molten salt containing at least one of potassium nitrate, rubidium nitrate, and cesium nitrate may be used. Furthermore, when replacing the potassium ions contained in the glass plate 110 with larger alkali metal ions, a molten salt containing at least one of rubidium nitrate and cesium nitrate may be used.

By chemically strengthening the glass plate 110, a compressive stress layer can be formed on the first main surface 112 and the second main surface 114 of the glass plate 110. The strength of the main surface 114 of 2 can be increased. The thickness of the compressive stress layer corresponds to the penetration depth of the displacing alkali metal ions. For example, when potassium nitrate is used to replace sodium ions with potassium ions, the thickness of the compressive stress layer can be 8 μm to 27 μm in soda lime glass, and the thickness of the compressive stress layer in aluminosilicate glass is 10 μm to 100 μm. can be In the case of aluminosilicate glass, the penetration depth of alkali metal ions is preferably 10 μm or more, more preferably 20 μm or more.

Here, the above-described in-plane void regions 130, 131, 132 and internal void rows 150 are formed in the glass plate 110 before the chemical strengthening treatment by the above-described laser irradiation step (step S110). Therefore, when the glass plate 110 is chemically strengthened, molten salt is introduced into the glass plate 110 through the surface voids 138 and the voids 158 .

As a result, the strength of the exposed surfaces (first main surface 112, second main surface 114, and end surface 116) of glass plate 110 as well as imaginary end surfaces can be increased by the chemical strengthening treatment.

FIG. 8 is a diagram schematically showing the concentration profile of introduced ions in the “in-plane direction” (the thickness direction of the glass plate 110; see the Z direction in FIG. 3) of the imaginary end face.

Here, the “introduced ions” refer to alkali metal ions introduced into the glass plate 110 by the chemical strengthening treatment, that is, impart a compressive stress layer to the first main surface 112 and the second main surface 114 of the glass plate 110. and alkali metal ions for increasing the strength of these main surfaces.

In FIG. 8, the horizontal axis is the relative position t (%) in the thickness direction of the glass plate 110, the first main surface 112 side corresponds to t=0%, and the second main surface 114 side corresponds to t = 100%. The vertical axis is the concentration C of the introduced ions. However, this concentration C is an alkali metal of the same kind as the introduced ions contained in the portion other than the first main surface 112, the second main surface 114, and the end surface 116 of the glass plate 110, that is, the bulk portion of the glass plate 110. It is calculated by subtracting the concentration of ions.

As shown in FIG. 8, on the imaginary end face, the concentration C of introduced ions along the thickness direction of the glass plate 110 has a profile larger than the concentration (bulk concentration) of the bulk portion over the entire imaginary end face. It shows a parabolic profile. That is, the concentration C of the introduced ions shows a maximum value _Cmax on the first main surface 112 side (t=0%) and on the second main surface 114 side (t=100%), and in the depth direction The central portion (t=50%) tends to show the minimum value C _min . Here, the minimum value C _min >0.

Note that the shape of the concentration profile of the introduced ions varies depending on the thickness and material of the glass plate 110, the conditions of the chemical strengthening treatment, etc., but in any case, the concentration in the entire imaginary end surface is higher than that in the bulk portion. , as an example, produces such a substantially parabolic profile. However, due to the influence of the method of chemical strengthening treatment, etc., the introduced ion concentration C are often not exactly the same. That is, it is well recognized that only the concentration C on either major surface becomes _Cmax . In addition, unlike the mathematical definition of a parabola, the substantially parabolic profile here means that the concentration C of the introduced ions is different from the central portion in the thickness direction on the first main surface side and the second main surface side. The introduced ion concentration in this concentration profile, which is greater on the side of the major surface, refers to a profile that is higher than the bulk concentration of the glass article. For this reason, the substantially parabolic profile includes a profile in which the concentration of introduced ions is higher than the bulk concentration of the glass article, and a substantially trapezoidal profile in which the introduced ions C change relatively gently in the central portion in the thickness direction. Contains profiles.

Thus, in the first manufacturing method, the imaginary end faces can also be chemically strengthened.

Note that this chemical strengthening treatment is a step that is performed when necessary, and may be omitted. Also, the chemical strengthening treatment may be performed before the above-described laser irradiation step (step S110). However, in that case, it should be noted that the regions to be strengthened by the chemical strengthening treatment are limited to the exposed surfaces (the first main surface 112, the second main surface 114, and the end surface 116), and the imaginary end surface is not strengthened. There is

(Step S120)
Next, an organic film is formed on the first main surface 112 or the second main surface 114 of the glass plate 110 . Here, as an example, a case where an organic film is formed on first main surface 112 of glass plate 110 will be described.

9 to 11 schematically show how the organic film 170 is formed on the first main surface 112 of the glass plate 110. FIG.

The organic film 170 is installed so as to cover at least the surface region of each glass piece (the surface corresponding to the first main surface 112 of the glass plate 110).

For example, in the example shown in FIG. 9, the organic film 170 covers the surface area of each glass piece 160a, and is placed on the first main surface 112 so that only the peripheral portion is exposed in a frame shape.

Also, in FIG. 10, the organic film 170 is installed so as to cover the surface region of each glass piece 160c and only the peripheral portion thereof is exposed in a frame shape. 10 differs from the embodiment of FIG. 9 in that the organic film 170 is also provided on the first main surface 112 of the glass plate 110 in a region other than the glass piece 160c.

Furthermore, in FIG. 11, the organic film 170 is placed in a plurality of regions so as to cover only the surface region of each glass piece 160c.

9 to 11 are merely examples, and the organic film 170 may be installed in any manner as long as it covers the surface regions of the glass pieces 160a to 160c. . In particular, organic film 170 is preferably formed over the entire surface of first main surface 112 . In this case, the masking process becomes unnecessary.

The organic film 170 may be, for example, a polymer having a siloxane bond as a main skeleton and containing F (fluorine).

An example of the chemical formula of such an organic film 170 is shown in the following formula (1).

ここで、反応基Ｒ_１およびＲ_２は、それぞれ独立に、Ｆ（フッ素）、Ｈ（酸素）、Ｃ（炭素）、およびＣ_ｎＨ_２ｎ－１（ｎ＝１～１００）からなる群から選定される。

wherein the reactive groups R ₁ and R ₂ are each independently selected from the group consisting of F (fluorine), H (oxygen), C (carbon), and C _n H _2n-1 (n=1-100) be done.

When an organic film having such a reactive group is used, first main surface 112 of glass plate 110 can develop water repellency.

The thickness of the organic film 170 is, but not limited to, in the range of, for example, 1 nm to 1 μm, and in the case of an F (fluorine)-based organic film, the thickness is preferably 1 nm to 10 nm.

A method for forming the organic film 170 is not particularly limited. The organic film 170 may be deposited by conventional deposition techniques such as, for example, sputtering, vapor deposition, and coating.

Note that one or more functional films may be formed on the first main surface 112 of the glass plate 110 before the organic film 170 is formed. For example, an antireflection film may be formed on the first main surface 112 of the glass plate 110 . An antireflection film is usually formed by alternately laminating a plurality of oxide layers having different refractive indices. Alternatively, a functional film other than the antireflection film may be installed.

(Step S130)
The glass article is then separated from the glass plate 110 .

In this separation step, a laser different from the laser in step S110 (hereinafter referred to as "another laser") is used. Another laser is irradiated to the main surface of glass plate 110 on which organic film 170 is formed (hereinafter referred to as "film formation surface") in the film formation step (step S120) described above. Note that the other laser irradiation surface may be a surface other than the film formation surface. For example, when a black film or the like is formed on the surface other than the film forming surface, it is preferable to irradiate the film forming surface.

Other lasers include, for example, solid state lasers, gas lasers, semiconductor lasers, or free electron lasers. Examples of solid-state lasers include YAG lasers. Examples of gas lasers include CO ₂ lasers, excimer lasers, Ar lasers and He--Ne lasers.

The imaginary end surface 165 formed on the glass plate 110 in the above step (step S110) has a plurality of surface voids 138 and voids 158 included in the in-plane void region 130 and the corresponding internal void array 150. have. Therefore, in the separation process, these surface voids 138 and voids 158 play a role, so to speak, like "perforation".

That is, when the in-plane void region 130 (or its vicinity; the same shall apply hereinafter) is irradiated with another laser, heat from the other laser causes voids 158 forming the internal void row 150 near the irradiation position. They are connected to form a cutting line penetrating through the glass plate 110 in the depth direction. Therefore, when such another laser is scanned along the in-plane void region 130, the voids 158 in each internal void row 150 are connected to each other, and the internal void row 150 changes into a cutting line. Furthermore, the surface voids 138 forming the in-plane void regions 130 are also connected to each other, and cutting lines are also generated in the plane of the first main surface 112 .

As a result, the glass plate 110 is divided at the imaginary end surface 165 described above, thereby separating the glass article from the glass plate 110 .

As described above, in the first manufacturing method, one or more glass articles can be manufactured from the glass plate 110 through steps S110 to S130.

Here, when the glass plate is fused and cut by irradiating the glass plate with another laser by the method described in Patent Document 1, the glass article can be separated, but the organic film 170 is damaged at this time. may receive

On the other hand, in the first manufacturing method, in-plane void regions 130 and internal void arrays 150 are already formed in the glass plate 110 by step S110 before separation by another laser. Therefore, in the first manufacturing method, the glass articles can be separated relatively easily without irradiating another high-energy laser that melts the glass plate 110 .

Specifically, in the first manufacturing method, the separate laser used in step S130 irradiates the film formation surface under irradiation conditions that satisfy the following conditions:
In the separated organic film of the glass article, when the in-plane central part is MC and one point on the end surface of the glass article is MP when viewed from the top (however, when the glass article is approximately polygonal, MP is 2 are selected from the points excluding the intersection of the edges),
In the MP, the count number of fluorine obtained by the X-ray photoelectric spectroscopy (XPS) method is I _MP (F), the count number of silicon is I _MP (Si), and I _MP (F)/I _MP (Si) is _RMP , and
At the point MC, the count number of fluorine obtained by the X-ray photoelectric spectroscopy (XPS) method is I _MC (F), the count number of silicon is I _MC (Si), and I _MC (F)/I _MC ( When Si) is _RMC ,

Ratio R _MP /R _MC ≧0.3

meet.

The irradiation energy within the spot diameter is not necessarily uniform within the spot diameter. For example, the central portion of the spot diameter range may have lower energy than the peripheral portion, and vice versa. Therefore, the facet at the MP includes not only the facet but also the range of spot diameters on the organic film of another laser near the facet, and I _MP (F) is the range of the facet and this spot diameter. represents the minimum value. The same applies to MP and I _MP (F) described below.

When the glass plate 110 is irradiated with another laser under such irradiation conditions, the influence on the organic film 170 can be significantly suppressed.

As a result, in the first manufacturing method, the film-forming surface of the glass plate 110 is irradiated with another laser, and the other laser is scanned along the in-plane void region 130, so that the organic film 170 is not significantly affected. It is possible to separate the glass article from the glass plate 110 without affecting the glass.

In order to obtain the irradiation conditions as described above, the type of laser, the power of laser irradiation, the scanning speed, the spot diameter, and the like may be adjusted. For example, if the other laser is a YAG laser, more energy is required because glass has a lower absorption rate of laser energy than a _CO2 laser.

(Method for producing another glass article according to one embodiment of the present invention)
Next, another method for manufacturing a glass article according to one embodiment of the present invention will be described with reference to FIG.

FIG. 12 schematically shows the flow of another method for manufacturing a glass article (hereinafter referred to as "second manufacturing method") according to one embodiment of the present invention.

As shown in FIG. 12, the second manufacturing method includes:
(1) A film-forming step of forming an organic film on the first main surface of a glass plate having a first main surface and a second main surface facing each other (step S210). When,
(2) a laser irradiation step (step S220) of irradiating a laser from the first main surface side of the glass plate;
(3) a separation step (step S230) of scanning a laser different from the laser from the first main surface side of the glass plate to separate one or more glass articles from the glass plate;
have

Each step will be described below. For clarity, the reference numerals shown in FIGS. 2 to 11 used in the explanation of the first manufacturing method are also used in the following explanation when representing each member and portion.

(Step S210)
First, a glass plate 110 having a first major surface 112 and a second major surface 114 facing each other is prepared.

The glass plate 110 may have a form as shown in FIG. 2 above.

Next, if necessary, the glass plate 110 may be chemically strengthened. However, in the second manufacturing method, the regions to be strengthened by the chemical strengthening treatment are limited to the exposed surfaces (the first main surface 112, the second main surface 114, and the end surface 116). ) is not reinforced.

Next, an organic film 170 is formed on the first main surface 112 of the glass plate 110 .

The specifications of the organic film 170, the film forming method, the film forming position, and the like have been described in detail in the above-described first manufacturing method. Therefore, detailed description is omitted here.

As described above, organic film 170 is preferably formed over the entire first main surface 112 of glass plate 110 . The main surface of the glass plate 110 on which the organic film 170 is formed is hereinafter also referred to as a "film formation surface".

(Step S220)
Next, the film formation surface of the glass plate 110 is irradiated with a laser. It should be noted that the laser used here is different from the laser used in the subsequent separation step (step S230).

In-plane void regions 130 are formed in the film-forming surface of the glass plate 110 , that is, the first main surface 112 by laser irradiation. Also, a plurality of internal void rows 150 are formed downward from this in-plane void region 130 toward the second main surface 114 .

As described above, the plane including the in-plane void regions 130 and the internal void rows 150 corresponding to the in-plane void regions 130 is referred to as the imaginary end surface 165 . This imaginary end face 165 substantially corresponds to the end face of the glass article manufactured by the second manufacturing method.

(Step S230)
Next, a separation step is performed to separate the glass article from the glass plate 110 .

In this separation step, a laser different from the laser (hereinafter referred to as "another laser") is used. Note that the other laser is irradiated to the film formation surface side of the glass plate 110 .

As described above, another laser irradiation and scanning causes the glass plate 110 to be cut at the imaginary end surface 165 described above, thereby separating one or more glass articles from the glass plate 110 .

Also in the second manufacturing method, in-plane void regions 130 and internal void arrays 150 are already formed in the glass plate 110 by step S220 before separation by another laser. Therefore, in the second manufacturing method, the glass articles can be separated relatively easily without irradiating a high-energy laser that melts the glass plate 110 .

Specifically, in the second manufacturing method, the separate laser used in step S230 irradiates the film formation surface under irradiation conditions satisfying the following conditions:
In the separated organic film of the glass article, when the in-plane central part is MC and one point on the end surface of the glass article is MP when viewed from the top (however, when the glass article is approximately polygonal, MP is 2 are selected from the points excluding the intersection of the edges),
In the MP, the count number of fluorine obtained by the X-ray photoelectric spectroscopy (XPS) method is I _MP (F), the count number of silicon is I _MP (Si), and I _MP (F)/I _MP (Si) is _RMP , and
At the point MC, the count number of fluorine obtained by the X-ray photoelectric spectroscopy (XPS) method is I _MC (F), the count number of silicon is I _MC (Si), and I _MC (F)/I _MC ( When Si) is _RMC ,

Ratio R _MP /R _MC ≧0.3

meet.

When the glass plate 110 is irradiated with another laser under such irradiation conditions, the influence on the organic film 170 can be significantly suppressed.

As a result, in the second manufacturing method, the deposition surface of the glass plate 110 is irradiated with another laser, and the other laser is scanned along the in-plane void region 130, thereby significantly affecting the organic film 170. It is possible to separate the glass article from the glass plate 110 without affecting the

Further, when separating the glass article from the glass plate 110, the value of the contact angle of the organic film with respect to water droplets at the _MP is defined as TMP,
When TMC is the contact angle of the organic film with respect to the water droplet at the point _MC ,

_TMP / _TMC ≥ 0.90

It is preferable to irradiate another laser so as to satisfy

When the glass plate 110 is irradiated with another laser under such irradiation conditions, the glass article can be separated without impairing the water repellency of the organic film 170 .

The method for manufacturing a glass article according to one embodiment of the present invention has been described above using the first and second manufacturing methods as examples. However, these are merely examples, and in the present invention, further manufacturing methods may be applied. For example, some steps may be modified or changed in the first and second manufacturing methods, and/or additional steps may be added to the first and second manufacturing methods.

In addition, in the first and second manufacturing methods, since a plurality of in-plane voids are formed in the glass plate, high energy as in the conventional art is not required when separating the glass article from the glass plate. Therefore, in some cases, the glass article can be separated simply by applying hot air to the glass plate without using a laser. However, in this case, it is more difficult to control the hot air for separating the glass article according to its shape than with a laser. This is because when hot air is used, the temperature distribution of the glass plate in the hot air is wider than when using a laser.

(Glass article according to one embodiment of the present invention)
Next, a glass article according to one embodiment of the present invention will be described with reference to FIGS. 13 and 14. FIG.

FIG. 13 shows a schematic perspective view of a glass article according to one embodiment of the present invention (hereinafter referred to as "first glass article"). Also, FIG. 14 shows a schematic cross-sectional view of the first glass article along line AA of FIG.

As shown in FIGS. 13 and 14, the first glass article 300 has a first major surface 302 and a second major surface 304 facing each other and an end surface connecting the two.

In the example of FIG. 13, the first glass article 300 has a generally rectangular shape and has four end faces 306-1 to 306-4. Further, each end surface 306-1 to 306-4 extends parallel to the thickness direction (Z direction) of the first glass article 300. As shown in FIG.

As clearly shown in FIG. 14, the first glass article 300 has a glass substrate 320 and an organic film 370 . The glass substrate 320 has a first major surface 322 and a second major surface 324 facing each other, and an end surface 326 connecting the two. The organic film 370 is arranged on the first main surface 322 side of the glass substrate 320 .

First major surface 302 of first glass article 300 corresponds to the surface of organic film 370 , and second major surface 304 of first glass article 300 corresponds to second major surface 324 of glass substrate 320 . handle. Each of the four end faces 306-1 to 306-4 of the first glass article 300 is composed of one end face 326 of the glass substrate 320 and the corresponding end face 372 of the organic film 370. As shown in FIG.

In addition, in the examples shown in FIGS. 13 and 14, the first glass article 300 has a substantially rectangular shape.

However, this is merely an example, and various forms are envisioned as the form of the first glass article 300 . For example, the shape of the first glass article 300 may be a rectangular shape, a triangle, a polygon with pentagons or more, a circle, or an ellipse. Also, in the case of a polygon, each corner portion may be rounded.

Also, the number of end surfaces of the first glass article 300 may be, for example, one, three, or four or more, depending on the configuration of the first major surface 302 and the second major surface 304. . Furthermore, the end surface of the first glass article 300 may extend obliquely from the Z direction (ie, in a direction non-parallel to the Z direction). In this case, a "slanted" end face is obtained.

The thickness of the first glass article 300 is not particularly limited. The thickness of the first glass article 300 may range, for example, from 0.03 mm to 6 mm.

Here, in the first glass article 300, the organic film 370 is characterized in that it is properly present even at the positions of the end faces 306-1 to 306-4 of the first glass article 300 when viewed from above. That is, when viewed from above, the thickness of the organic film 370 at the positions of the end surfaces 306-1 to 306-4 is thin compared to the central portion of the first glass article 300, but it is not zero. .

This is a significant feature not available with conventional manufacturing methods such as cutting glass sheets with high energy lasers to separate glass articles. This is because, in the glass article manufactured by the conventional method, the organic film is damaged by the heat from the laser, and hardly remains on the divided surface, that is, the end surface.

Such characteristics can be obtained in the first glass article 300 by manufacturing it using, for example, the first manufacturing method or the second manufacturing method described above.

In particular, the organic film 370 has a substantially central portion MC (see FIG. 13) and one point on the end faces 306-1 to 306-4 of the first glass article 300 MP (see FIG. 13). However, when the first glass article 300 is substantially polygonal, MP is selected from points excluding the intersection of two sides),
At the point MP, the count number of fluorine obtained by the X-ray photoelectric spectroscopy (XPS) method is I _MP (F), the count number of silicon is I _MP (Si), and I _MP (F)/I _MP (Si) is _RMP , and
At point MC, the count number of fluorine obtained by the X-ray photoelectric spectroscopy (XPS) method is I _MC (F), the count number of silicon is I _MC (Si), and I _MC (F)/I _MC (Si ) as _RMC ,

Ratio R _MP /R _MC ≧0.3

meet.

here,

Ratio R _MP /R _MC <1

is.

Thus, in the first glass article 300 , the organic film 370 can be arranged over the entire first main surface 302 of the first glass article 300 with little damage to the cut portion of the organic film 370 .

(other features)
(Organic film 370)
The polymer structure, chemical formula, film thickness, etc. of the organic film 370 are the same as those of the organic film 170 described above. When the organic film 370 is used, the first main surface 302 of the first glass article 300 can develop water repellency.

In particular, in order not to impair the water repellency, the value of the contact angle of the organic film with respect to water droplets at the _MP is defined as TMP,
When TMC is the contact angle of the organic film with respect to the water droplet at the point _MC ,

_TMP / _TMC ≥ 0.90

is preferably irradiated so as to satisfy

(Chemical strengthening)
In the first glass article 300, the glass substrate 320 may be chemically strengthened. In this case, in addition to the first major surface 322 and the second major surface 324, the end surface 326 may also be chemically strengthened.

However, in this case, the first main surface 322 and the second main surface 324 of the glass substrate 320 and the end surface 326 are in a chemically strengthened state, that is, introduced ions (alkali metal ions introduced by the chemical strengthening treatment). The state of distribution is different.

For example, in the glass substrate 320, the end face 326 has a substantially parabolic concentration profile of introduced ions from the first major surface 322 to the second major surface 324 as shown in FIG. 8 above. may

Such a concentration profile of introduced ions can be obtained when chemical strengthening treatment is performed between steps S110 and S120 in the above-described first manufacturing method to manufacture the first glass article 300. .

In contrast, as described above, when the chemical strengthening treatment is performed at the stage of the large glass plate, the first main surface 322 and the second main surface 324 of the glass substrate 320 are strengthened, but the end surface 326 is strengthened. is not strengthened.

The configuration example of the first glass article 300 has been described above with reference to FIGS. 13 and 14 .

The first glass article 300 is, for example, electronic equipment (for example, information terminal equipment such as smartphones and displays), camera and sensor cover glass, architectural glass, industrial transportation glass, and biomedical glass equipment. can be applied.

For example, if the first glass article 300 is a cover glass, the organic film 370 may be an anti-fingerprint film (AFP). Also in this case, additional layers such as anti-reflection coatings may be included between the glass substrate 320 and the organic film 370 . The antireflection coating may have a repeating structure of multiple oxide layers.

Examples of the present invention will be described below.

(Example I)
In the following description, Examples 1 to 5 are working examples, and Examples 11 to 12 are comparative examples.

(Example 1)
Steps S120 and S130 in the above-described first manufacturing method were carried out in order to prepare samples for evaluation.

Note that step S110 was not performed. This is because once the glass article has been separated from the glass plate by carrying out all steps S110 to S130, the subsequent evaluation of the organic film (water repellency evaluation and XPS analysis) will be performed at the tip of the end face portion of the glass article. This is because it becomes necessary to carry out the analysis at , and the analysis operation becomes complicated. Conversely, in the case of the glass plate that has undergone only steps S120 and S130, the glass plate has not yet been separated. Therefore, it is sufficient to evaluate the region of the organic film irradiated with the laser in step S130, making the evaluation of the organic film easier. can be implemented. It is clear that the results obtained with such an evaluation are substantially equivalent to the results obtained with the edges of the glass articles separated by the first manufacturing method.

First, as a glass plate, a raw plate of aluminosilicate glass Dragontrail (registered trademark) before chemical strengthening was prepared. The dimensions of the glass plate are 100 mm long×100 mm wide×0.8 mm thick.

Next, an antireflection film and an organic film were sequentially formed over one main surface (first main surface) of the glass plate.

The antireflection film has a four-layer structure of Nb ₂ O ₅ (target thickness 15 nm)/SiO ₂ (target thickness 35 nm)/Nb ₂ O ₅ (target thickness 120 nm)/SiO ₂ (target thickness 80 nm), A film was formed by a sputtering method.

An anti-fingerprint film (KY185: manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the organic film, and was formed by vapor deposition. The target thickness of the organic film was set to 4 nm.

Next, the side of the first main surface of the glass plate was irradiated with a CO ₂ laser. This CO ₂ laser corresponds to the "another laser" used in the "separation step" (step S130) in the first manufacturing method described above.

The irradiation conditions of the _CO2 laser are as follows:

Output Q=38.7W,
spot diameter φ=3 mm,
Scanning speed v=30 mm/sec

This spot diameter is the width of a working mark produced when a 5 mm thick acrylic plate is irradiated with laser at an output of 38.7 W and a laser scanning speed of 70 mm/sec. At this time, the distance from the laser condensing lens to the acrylic plate is made farther than the distance at which the spot diameter is the smallest, and the focal point is shifted with respect to the surface of the acrylic plate. Even in the case of different spot diameters, the spot diameter is set to the width of the processing mark of the 5 mm thick acrylic plate based on the predetermined output and scanning speed.

This produced a sample for evaluation.

(evaluation)
Using the sample manufactured by the above-described method (hereinafter referred to as "sample according to Example 1"), the following evaluations were performed.

(Evaluation of water repellency of organic film)
The water repellency of the surface of the organic film of the sample according to Example 1 was evaluated. Water repellency was evaluated by dropping a water droplet having a volume of 1 to 3 μL on the organic film and measuring the contact angle of the water droplet. DMo-701 manufactured by Kyowa Interface Science Co., Ltd. was used for the measurement.

The evaluation was carried out at two locations: a substantially central portion of the organic film (hereinafter referred to as “central region”) and a region of the organic film irradiated with the CO ₂ laser (hereinafter referred to as “target irradiated region”).

As a result of the measurement, in the central region of the organic film, the water repellency was so strong that water droplets were repelled, and the contact angle could not be measured. On the other hand, the contact angle of the target irradiated region of the organic film was 113.2°, which is a sufficiently large value.

From this, it was confirmed that in the sample according to Example 1, the function of the organic film was not impaired even in the CO ₂ laser irradiation region.

(XPS analysis of organic film)
Next, in the sample according to Example 1, an X-ray photovoltaic spectroscopy (XPS) analysis of the organic film was performed. The analysis was performed at predetermined intervals along the central region of the organic film from the target irradiated region of the organic film. For the measurement, Quantera SXM manufactured by PHI was used, and the probe diameter was 2 mmφ, the measurement time was 0.2 minutes/cycle, the pass energy was 224.0 eV, the step energy was 0.4 eV, and the sample angle was 45°.

FIG. 15 shows an example of XPS analysis results.

In FIG. 15, the horizontal axis represents the distance from the target irradiated region of the organic film, and the distance 0 corresponds to the target irradiated region of the organic film. That is, the horizontal axis represents the distance from the target irradiated region in the direction of the straight line connecting the target irradiated region and the central region of the organic film. On the other hand, the vertical axis of FIG. 15 represents the count ratio F/Si of F (fluorine) and Si (silicon).

As shown in FIG. 15, the count number ratio F/Si was lowest (12.8) near the distance 0, and showed a tendency to gradually increase as the distance increased. From FIG. 15, when the distance exceeds 4 mm, the ratio F/Si showed a value of 25.9 as an average value from 10 to 20 distances.

As described above, since the ratio F/Si is not 0 even at the point where the distance is 0, it was confirmed that in the sample according to Example 1, the organic film was present even in the target irradiated region.

Here, the count number of fluorine in the target irradiated region is designated as I _AP (F), the count number of silicon is designated as I _AP (Si), and I _AP (F)/I _AP (Si) is expressed as R _AP . Also, the count number of fluorine in the central region is I _AC (F), the count number of silicon is I _AC (Si), and I _AC (F)/I _AC (Si) is represented as R _AC .

Calculating based on this notation, the ratio R _AP /R _AC for the sample according to Example 1 was 0.49.

It should be clear that this ratio R _AP /R _AC substantially corresponds to the aforementioned ratio R _MP /R _MC , assuming that the glass article is separated from the glass plate.

(Examples 2 to 5)
A sample for evaluation was produced in the same manner as in Example 1.

However, in Examples 2 to 5, irradiation conditions different from those in Example 1 were selected as the irradiation conditions of the CO ₂ laser.

Using the obtained samples (samples according to Examples 2 to 5), the same evaluation as in Example 1 was performed.

(Example 11 to Example 12)
A sample for evaluation was produced in the same manner as in Example 1.

However, in Examples 11 and 12, irradiation conditions different from those in Example 1 were selected as the irradiation conditions of the CO ₂ laser.

Using the obtained samples (samples according to Examples 11 and 12), the same evaluation as in Example 1 was performed.

Table 1 below summarizes the CO ₂ laser irradiation conditions in each example and the evaluation results obtained for the samples according to each example.

表１の結果から、例１～例５では、比Ｒ_ＡＰ／Ｒ_ＡＣが０．３を超えており、有機膜は、サンプルのＣＯ_２レーザが照射された領域にも、実質的に相当量残存していることがわかった。この結果は、サンプルの対象被照射領域においても、１００゜を超える大きな接触角が得られている結果（表１の接触角（°）「Ｔ_ＡＰ」欄参照）とも対応する。

From the results in Table 1, in Examples 1 to 5, the ratio R _AP /R _AC exceeds 0.3, and the organic film is substantially even in the CO ₂ laser irradiated region of the sample. found to remain. This result also corresponds to the result that a large contact angle exceeding 100° was obtained even in the target irradiated region of the sample (see contact angle (°) “T _AP ” column in Table 1).

Thus, in the samples according to Examples 1 to 5, it was confirmed that the organic films were not damaged or lost much during the CO ₂ laser irradiation. From this, it can be said that in the first manufacturing method described above, the glass article can be properly separated after the separation step is performed.

On the other hand, in the samples according to Examples 11 and 12, the ratio R _AP /R _AC was less than 0.3, indicating that the organic film did not largely remain in the CO ₂ laser irradiation region. This result also corresponds to the fact that the contact angle is greatly reduced (less than 100°) in the target irradiated area of the sample.

As described above, in the samples according to Examples 11 and 12, assuming the first manufacturing method, the edges of the organic film were damaged and lost during the separation process by CO ₂ laser irradiation, and the organic film was removed. It is believed that the glass articles cannot be separated under proper conditions.

Here, assuming that the value of the contact angle of the organic film with respect to the water droplet in the target irradiation region is T _AP , and the value of the contact angle of the organic film with respect to the water droplet in the central region is T _AC , the samples according to Examples 2 to 5 , T _AP /T _AC was 0.90 or more. On the other hand, in the samples according to Examples 11 and 12, T _AP /T _AC was less than 0.90.

Assuming that the glass article is separated from the glass plate, it will be clear that this ratio _TAP / _TAC substantially corresponds to the aforementioned ratio _TMP / _TMC .

(Example 15)
In the above examples, step S110 was not performed in the first manufacturing method. Therefore, in order to confirm that the glass article can be separated from the glass plate by implementing the first manufacturing method, the following experiment was conducted.

The first major surface of the glass sheet was irradiated with a laser to form a plurality of in-plane void regions and corresponding rows of internal voids in the glass sheet. The same glass plate as used in Example 1 was used as the glass plate.

As the device, a burst laser (3 pulses) manufactured by Rofin (Germany) capable of emitting a short pulse laser of the order of picoseconds was used. The laser output was 90% of the rated (50 W). The frequency of one laser burst is 60 kHz, the pulse width is 15 picoseconds, and the burst width is 66 nanoseconds. Each in-plane void was defined as a “single-line in-plane void region”. Also, the in-plane void regions were arranged in a substantially grid pattern as shown in FIG. The center-to-center distance between the in-plane voids forming the in-plane void region was set to about 4 μm to 6 μm.

Next, under the same conditions as the CO ₂ laser irradiation conditions in Example 1, a CO ₂ laser was irradiated along the in-plane void regions.

In addition, in Example 15, no organic film was formed. However, it has been confirmed from the evaluation results of the sample according to Example 1 that the organic film is hardly damaged by the CO ₂ laser irradiation.

After irradiation with the _CO2 laser, the glass article could be separated from the glass plate.

Next, the same experiment was conducted by changing the irradiation conditions of the CO ₂ laser to those adopted in Examples 2-5. As a result, it was confirmed that the glass article could be separated from the glass plate after the CO ₂ laser irradiation under any of the CO ₂ laser irradiation conditions.

(Example II)
In the following description, Examples 21-25 and 31-34 are examples, and Examples 26, 35 and 36 are comparative examples.

(Example 21)
In order to prepare samples for evaluation, Steps S110 to S130 in the first manufacturing method were carried out as follows.

First, as a glass plate, the same glass plate as in Example I was prepared. The dimensions of the glass plate are 100 mm long×100 mm wide×0.8 mm thick.

Next, a laser was irradiated from one main surface (first main surface) of the glass plate under the following conditions to form a plurality of in-plane void regions and internal void arrays in the glass plate.

As a laser device, a burst laser (with 3 pulses) manufactured by Rofin (Germany) capable of emitting a short pulse laser on the order of picoseconds was used. The laser output was 90% of the rated (50 W). The frequency of one laser burst is 60 kHz, the pulse width is 15 picoseconds, and the burst width is 66 nanoseconds.

Each in-plane void region was defined as a “single-line in-plane void region”. Also, the in-plane void regions were arranged in a substantially grid pattern as shown in FIG. The center-to-center distance between the surface voids forming the in-plane void region was set to about 4 μm to 6 μm.

Next, an antireflection film and an organic film were sequentially formed over the entire first main surface of the glass plate.

The antireflection film has a four-layer structure of Nb ₂ O ₅ (target thickness 15 nm)/SiO ₂ (target thickness 35 nm)/Nb ₂ O ₅ (target thickness 120 nm)/SiO ₂ (target thickness 80 nm), A film was formed by a sputtering method.

An anti-fingerprint film (Afuid S550: manufactured by Asahi Glass Co., Ltd.) was used as the organic film and formed by a vapor deposition method. The target thickness of the organic film was set to 4 nm.

Next, the side of the first main surface of the glass plate was irradiated with a CO ₂ laser. This CO ₂ laser corresponds to the "another laser" used in the "separation step" (step S130) in the first manufacturing method described above.

The irradiation conditions of the _CO2 laser are as follows:

Output Q=38.7W,
spot diameter φ=3 mm,
Scanning speed v=50 mm/sec

As in Example I, this spot diameter is the width of a working mark produced when a 5 mm thick acrylic plate is irradiated with laser at an output of 38.7 W and a laser scanning speed of 70 mm/sec.

After irradiation with the _CO2 laser, the glass article was separated from the glass plate. One of the obtained glass articles was recovered and used as a sample for evaluation below (referred to as "sample according to Example 21").

(Examples 22 to 25)
A sample for evaluation was produced in the same manner as in Example 21.

However, in these Examples 22 to 25, irradiation conditions different from those in Example 21 were selected as the irradiation conditions of the CO ₂ laser.

The samples obtained are referred to as "samples according to Examples 22 to 25", respectively.

(Example 26)
A sample for evaluation was produced in the same manner as in Example 21.

However, in Example 26, irradiation conditions different from those in Example 21 were selected as irradiation conditions for the CO ₂ laser.

The resulting sample is referred to as "Sample according to Example 26".

(Example 31)
A sample for evaluation was produced in the same manner as in Example 21 above.

However, in Example 31, the organic film placed on the first surface of the glass plate was changed from that in Example 21. Specifically, an anti-fingerprint film (Afuid S550: manufactured by Asahi Glass Co., Ltd.) was used as the organic film and formed by a spray method. The target thickness of the organic film was set to 5 nm.

After irradiation with the _CO2 laser, the glass article was separated from the glass plate. One of the obtained glass articles was collected and used as a sample for evaluation below (referred to as "sample according to Example 31").

(Examples 32 to 34)
A sample for evaluation was produced in the same manner as in Example 31.

However, in these Examples 32 to 34, different irradiation conditions from those in Example 31 were selected as the irradiation conditions of the CO ₂ laser.

The resulting samples are referred to as "Samples according to Examples 32-34", respectively.

(Examples 35 and 36)
A sample for evaluation was produced in the same manner as in Example 31.

However, in these Examples 35 and 36, different irradiation conditions from those in Example 31 were selected as the irradiation conditions of the CO ₂ laser.

The samples obtained are referred to as "Samples according to Examples 35 and 36", respectively.

(evaluation)
The following evaluations were performed using each sample manufactured by the method described above.

(Evaluation of water repellency of organic film)
The water repellency of the surface of the organic film of the samples according to Examples 21 to 26 and Examples 31 to 36 was evaluated. The water repellency evaluation method is the same as in Example I.

However, in Example II, the water repellency was measured in the central portion of the organic film on the first surface of the sample and the position 500 μm inside from the laser-cut end surface of one of the organic films (corresponding to the above-mentioned “target irradiation area”). ) was regarded as the end face and measured. The contact angle at each position is represented by " _TAP " and " _TAC ".

(XPS analysis of organic film)
X-ray photovoltaic spectroscopy (XPS) analysis of the organic film was performed on each sample. The analytical method is the same as in Example I.

However, in Example II, the position 500 μm inside from the laser-cut end face (corresponding to the above-mentioned “target irradiated region”) is regarded as the end face, and from this position, along the central portion of the organic film, a predetermined interval XPS analysis was performed at

Here, the count number of fluorine in the target irradiated region is designated as I _AP (F), the count number of silicon is designated as I _AP (Si), and I _AP (F)/I _AP (Si) is expressed as R _AP . Also, the count number of fluorine in the central portion is I _AC (F), the count number of silicon is I _AC (Si), and I _AC (F)/I _AC (Si) is expressed as R _AC .

Table 2 summarizes the CO ₂ laser irradiation conditions for the samples according to Examples 21 to 26 and the evaluation results obtained for the samples according to each example.

表２の結果から、例２１～例２５では、比Ｒ_ＡＰ／Ｒ_ＡＣが０．３を超えており、有機膜は、サンプルのＣＯ_２レーザが照射された領域にも、実質的に相当量残存していることがわかった。この結果は、例２１～例２５の場合、サンプルの対象被照射領域においても、８９．５゜を超える大きな接触角が得られている結果とも対応する。

From the results in Table 2, in Examples 21 to 25, the ratio R _AP /R _AC exceeds 0.3, and the organic film is substantially even in the CO ₂ laser irradiated region of the sample. found to remain. This result also corresponds to the result that in the case of Examples 21 to 25, a large contact angle exceeding 89.5° was obtained even in the target irradiated area of the sample.

Thus, in the samples according to Examples 21 to 25, it was confirmed that the organic films were not damaged or lost much during the CO ₂ laser irradiation. From this, it can be said that in the first manufacturing method described above, the glass article can be properly separated after the separation step is performed.

On the other hand, in the sample according to Example 26, the ratio R _AP / _RAC was much lower than 0.3, indicating that the organic film did not remain much in the area irradiated with the CO ₂ laser. This result also corresponds with the fact that the contact angle is reduced to about 80° in the target irradiated area of the sample.

Table 3 summarizes the CO ₂ laser irradiation conditions for the samples according to Examples 31 to 36 and the evaluation results obtained for the samples according to each example.

表３の結果から、例３１～例３４では、比Ｒ_ＡＰ／Ｒ_ＡＣが０．３を超えており、有機膜は、サンプルのＣＯ_２レーザが照射された領域にも、実質的に相当量残存していることがわかった。この結果は、例３１～例３４では、サンプルの対象被照射領域において、１００゜を超える接触角が得られている結果とも対応する。

From the results in Table 3, in Examples 31 to 34, the ratio R _AP /R _AC exceeds 0.3, and the organic film is substantially even in the CO ₂ laser irradiated region of the sample. found to remain. This result is also consistent with the fact that Examples 31-34 provide contact angles of greater than 100° on the target irradiated area of the sample.

Thus, in the samples according to Examples 31 to 34, it was confirmed that the organic films were not damaged or lost much during the CO ₂ laser irradiation. From this, it can be said that in the first manufacturing method described above, the glass article can be properly separated after the separation step is performed.

On the other hand, in the samples according to Examples 35 and 36, the ratio R _AP /R _AC was less than 0.3, indicating that the organic film did not largely remain in the CO ₂ laser irradiation region. This result also corresponds to the fact that the contact angle is reduced (below 88.9°) in the target irradiated area of the sample.

This application claims priority based on Japanese Patent Application No. 2016-171296 filed on September 1, 2016, and the entire contents of the same Japanese application are incorporated herein by reference.

110 glass plate 112 first main surface 114 second main surface 116 end surface 130, 131, 132 in-plane void region 138 surface voids 138A, 138B surface void row 150 internal void row 158 voids 160a to 160c glass piece 165 imaginary end surface 170 Organic film 300 First glass article 302 First main surface 304 Second main surface 306-1 to 306-4 End surface 320 Glass substrate 322 First main surface 324 Second main surface 326 End surface 370 Organic film 372 Organic membrane edge

Claims (3)

A glass article having an organic film,
The glass article is
a glass substrate having first and second major surfaces facing each other and an end surface;
a fluorine-containing organic film disposed on the first main surface of the glass substrate;
has
The end surface of the glass substrate is chemically strengthened, and when the distance direction from the first main surface to the second main surface is referred to as the thickness direction,
In the chemically strengthened end face, the concentration profile of the predetermined alkali metal ions in the thickness direction is the lowest in the central portion in the thickness direction, and the first main surface side and the second main surface side. having a substantially parabolic profile in which the concentration is higher toward the main surface,
The predetermined alkali metal ions are alkali metal ions for imparting compressive stress layers to the first main surface and the second main surface to increase the strength of both main surfaces,
the minimum concentration of the predetermined alkali metal ions in the concentration profile at the end surface is higher than the bulk concentration of the glass substrate;
In the organic film, when the central portion on the side of the first main surface is MC, and one point on the end face in top view is MP (however, when the first main surface is substantially polygonal, MP is selected from points excluding the intersection of two sides),
In the MP, the count number of fluorine obtained by the X-ray photoelectric spectroscopy (XPS) method is I _MP (F), the count number of silicon is I _MP (Si), and I _MP (F)/I _MP (Si) is _RMP , and
In the MC, the count number of fluorine obtained by the X-ray photoelectric spectroscopy (XPS) method is I _MC (F), the count number of silicon is I _MC (Si), and I _MC (F)/I _MC (Si ) as _RMC ,

Ratio R _MP /R _MC ≧0.3

A glass article that satisfies 2. The glass article according to claim 1, wherein said organic film is a polymer having a siloxane bond as a main skeleton and containing F (fluorine). In the organic film,
Let TMP be the contact angle of the organic film with respect to the _MP ,
When TMC is the contact angle of the organic film with respect to the _MC ,

_TMP / _TMC ≥ 0.90

3. The glass article according to claim 1 or 2, which satisfies:

Images